Use of petroleum sulfonates in preparation of resinous condensation products in beadform



fatenteci Sept. 9,

ARATION OF RESINOUS CONDENSATION PRODUCTS IN BEAD FORM Lennart A. Lundberg, Stamford, Conn., assignor to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application February 17, 1949,

Serial No. 77,067 i i Claims.

This invention relates to ion exchange resins and more particularly, to the production of ion active resins in the form of spheroidal beads.

In the past, liquid polymerizable substances such as styrene, acrylic acid esters and the like have been polymerized in aqueous suspension to produce thermoplastic resins as granular products' uniform in composition and particle size. Similarly, spheroidal particles of gels have been prepared by gelation of hydrosols in water-immiscible media. Resins of the thermosetting condensation type such as urea-formaldehyde, melamine-formaldehyde and the like, and particularly resins of the thermosetting condensation type in a cured state such as the ion ex change resins, both anionic and cationic, have however not previously been produced inthe form of spheroidal particles or beads of uniform size.

It is an object of the present invention to produce a cation exchange resin active for the removal of cations from, or the exchange of cations in, fluid media in a form which can be used directly, without grinding or screening, in ion exchange processes.

Another object of the present invention is to produce an anion exchange resin active for the removal of anions from, or the exchange of anions in, fluid media in a form which can be used directly, without grinding or screening, in ion exchange processes. l i

It is another-object of the present invention to produce ion exchange resins in theform of spheroidal particles. 1

A further object of the present invention is to provide a method for preparing a condensation type, thermosetting, synthetic resin in the form of spheroidal beads.

Still another object of the present invention is to convert partially condensed water-soluble resins to cured, water-insoluble ion active resins in bead form.

It is still a further object of the present invention to prepare in bead form an ion exchange resin. 1

The above and other objects are attained by dispersing an aqueous syrup of a resinous partial condensation product of ingredients which, when fully condensed, produce an insoluble ion active resin, in an organic non-solvent medium by mechanical agitation and in the presence of an anionic surface active agent which is a petroleum sulfonate, and converting the partially condensed product of the dispersed globules thereby formed to an insoluble resin by heating.

The invention will be described in greater detail in conjunction with the specific examples in 2 a Y which proportions are given in parts by weight. It should be understood that the examples are merely illustrative and it is not intended that the scope of the invention be limited to the details therein set forth.

EXAMPLE 1 (1) 1475 parts of resin A syrup (specific gravity (2) 489 parts of o-dichlorbenzene (3) 0.8 part of the sodium salt of a sulfonated petroleum fraction having the empirical formula CzsHizsOsNa (2) and (3) are charged into a suitable vessel equipped with an anchor type stirrer, a water trap and means for indicating temperature. The mix is heated to C., the stirrer is adjusted to 150 R. P. M., and (1) is added rapidly. The resulting dispersion is refluxed for one hour at 97" C., 74 parts of water are removed azeotro lacsally, and refluxing is resumed for one hour at C. The resin beads obtained have the following size distribution: 0.2% on 20 mesh, 66.9% 20-40 mesh, 29.3% 40-60 mesh, and 3.4% through 60 mesh. The resin has a capacity of 18.8 kilograins as calcium carbonate per cubic foot of resin and a density of 19.7 pounds per cubic foot.

EXAMPLE2 The procedure of Example 1 is followed. except that 58.5 parts of water are azeotropically removed and the final reflux at C. is continued for four hours.

EXAMPLE 3 (1) parts of resin C syrup (2) 655 parts of o-dichlorbenzene (3) 0.33 parts [0.05% of the weight of (2)1013 the sodium salt of a sulfonated petroleum fraction having the empirical formula: C2sH42SO3Na (2) and (3) are charged into a vessel as in Example 1 and (1) is added rapidly at 90 C. The resulting dispersion is heated until 67 parts'of water are removed azeotropically, and it is then refluxed for four hours at 117 C. Semi-opaque, white, vitreous beads of resin having a capacity of 20.5 kilograins as calcium carbonate per cubic foot of resin and a density of 24.8 pounds per cubic foot are obtained in the following size distribution: 6.8% on 20 mesh, 31.7% 2040 mesh, 51.8% 40-60 mesha'n'd 9.7% through 60 mesh.

EXAMPLE 4 (1) 175 parts of resin D syrup (2) 655 parts of o-dichlorbenz'en'e' (3) 0.07 part [0.01% of the weight of (2)] of the sodium salt of a sulfonated petroleum fraction having the empirical formula: C2aI-I42SO3Na (2) and (3) are charged into a vessel as" in Example 1 except that the agitation rate is increased to 210 R. P. M., and (1) is added rapidly at 85 C. The resulting dispersion is first heated until 43 parts of water are removed and thenrefluxed for two hours atlll" C. opaque, white, semi-vitreous beads of resin having a capacity of 14.3 kilograi'nsas calcium carbonateper cubic foot ofresin and a density of 15.5 pounds-per cubic foot are obtained in the following size distribution: 2.6-%- on 20 mesh, 25.7% 20-40 mesh, 48.0 40-60 mesh and 23.7 through 60 mesh.

EXAMPLE 5 (1) 175 parts of resin E syrup ('2) 655 parts of o-dichlorbenzene (3) 0.03 part [0.005% of the weight of (2)] of the sodium salt of a sulfonated petroleum fraction having the empirical formula:

C2sH42SO3Na (2) and" (3) are charged'into'a suitable vessel as'in Example 1, the stirrer is adjusted to 210 R. P. M., and (1) is added rapidly at 54' C. The resulting dispersion is refluxed for 2.5 hours. Chalky, porous-beads of resin having a capacity of 9.9 kilograins as calcium carbonate per cubic foot of resin and a density of 10.3 pounds per oubicfoot are obtained in the following size distribution: 35.7% 20-40 mesh, 51.3%40-60 mesh aind"13'.0%- through 60 mesh.

EXAMPLE 6 (1) 175 parts of-resin F syrup (2) 381 parts of ethylene dichloride (3) 0.2 part [0.05% of 'the weight of (2)] of the sodium salt of a sulfonated petroleum fraction having the empirical formula: C2sH42SO3Na EXAMPLE "7 (1) 150 parts'of resin G syrup" :(2) 655 parts'of o-dichlorbenzene (3) 0.7 part [0.1% of the weight-of (2)]of the sodium salt of a sulfonated petroleum fraction having the empirical formula: C2BH42SO3N2.

(2) and (3) arecharged into a suitable vessel equipped with an anchor type stirrer, a water trap and means for indicating temperature. The mix is heated to 80 C. and the stirrer adjusted to amateof 175R. 13. M., whereupon (Dis added '4 rapidly. The resulting dispersion is refluxed for 18 hours at 107 C.

Reddish-brown beads of resin having a capacity of 7.8 kilograins as calcium carbonate per cubic foot of resin and 2416 pounds per'cubic foot are-obtained.

EXAMPLE 8 (1) 325 parts of resin G syrup (2;) 655-parts of o-dichlorbenzene (3). 1.3"parts" [0.2% of the weight of (2)] of the sodium salt of a sulfonated petroleum fraction havingv the empirical formula: C2eH42SOsNa The procedure of Example 1 is followed and the dispersion is refluxed for 3 hours at 107 C. The light brown, rigid bead of resin obtained areOVen-cured for 3 hours at C. and 18 hours at C. The cured resin has a capacity of 20.6 kilograins as calcium carbonate per cubic foot of resin and a density of 33.9 pounds per cubic'foot.

EXAMPLE- 9- (1') parts of resin H syrup (2) 585 parts of o-dichlorbenze'ne V 39.5 parts of toluene (3) 6.2 parts [1.0% of the weight of (2).] of the sodium salt of a sulfonated petroleum fraction having the empirical'formula: C26H42SO3N8} The procedureof- Example 7' is followed with an agitation rate of 540 R. P. M., except that 62 parts of waterare removed a'zeotropically' by heatingabout 0.5 hour prior to refluxing for 17 hours-at 150 C. The lumpy black powdery prodnot has a particle-size'ra'n'ge from 5-125'microns, the bulk being within a range of from 35-75 microns.

EXAMPLE 10 (1) 175' partsof'resin 1" syrup (specificgravity 1.3) (2) 45.9 parts ofo-dichlorbenzene (specific 59 parts of toluene gravity 1.27) (3) 5.2 parts [1% by weight of- (2)] of the sodium salt of a-sulfonated petroleum fraction having the empirical-formula: C2sH42SOsNa= The procedure-of Example-I is followed with 560 R. P. M. rate of agitation,.62.5-parts of water being removed by heating for 0.7 hour,-and the resin being cured by refluxing for 8 hours at 150 C. Resin particles of from 14-16 mesh are obtained.

Preparation of resin" A syrup (1) 189 parts of tetraethylenepehtamine (1.0 mols) (2) 277 parts of epichlorohydrin (3.0 mols) (3) 466 parts of water (2) is added'slowly to (l) and (3) with-cooling to maintain the temperature at 45-55 C. About 0.5 hour is required for the addition. The syrup is then maintained at 50 C. for' 0.75-1.5 hours.

Preparation" of resin B syrup (1') 440 parts of 28 aqueous a'mmonia-(TmOlS) (2) 260-parts of-water (3) 651 parts of epichlorhydrin (7 mols) (4) 112 partsof 50% aqueous-sodium hydroxide (1.4 mols) (1) and (2) are placed in a-suitable vessel equipped-with means for indicating temperature and means for agitation, and (3) and (4)- are added gradually as follows: i

fi g Remarks 22 add 150 parts of (3). i 40 clear; hold 5:2 0. by external cooling; dropwise addition of (3) started. 39 (3) all added; cooling discontinued. 50' pH 8.85:.2. 70 pH 8.25:.2. 80 pH 8.01.2. 85 .cool. 85 pH 8.05:.2. 85 pH 7.7:i:.2. 85 pH 7.53:.2. 80 pH 7.05:.2; cool to 20 C. 20 add (4); cool. 32 24 The resin syrup thus obtained has a viscosity of 4.95 minutes or 6.8 poises on #300 Ostwald viscosimeter, and a density of 1.12.

Preparation of resin syrup (1) is placed in a suitable vessel equipped with Preparation of resin D syrup The same procedure as forthe preparation of resin C syrup is followed except that the temperature during acidification is kept below C. to produce a less viscous syrup.

Preparation of resin E syrup Resin D syrup is heateduntil its viscosity is increased to 1.5 poises.

Preparation of resin F syrup The procedure of resin Cf syrup preparation is followed, using 126 parts of melamine, 406 parts of formalin, 183 parts of guanidine nitrate, 94 parts of water and 60.5 parts of sodium chloride.

Preparation of resin Gf syrup (1) 94 parts of phenol V (2) 108 parts'of 95.5% sulfuric acid 3) 101 parts of 37% aqueous formaldehyde (4) 63 parts of water a (1) is reacted witl'i(2) at 90-95 C. The reactlon mixture is cooled to below 50 0., and (3) and (4) are added dropwiseover a 22 minute period. The ensuing reaction which is very exothermic necessitates close attention in order to maintain the temperature below 50 C. The dark red syrup obtained has a specific gravity of about 1.27 and a viscosity close to 25 centipoises. i

refinement of petroleum stead of 63 parts, of water.

Z Q Preparation of. resin I. syrup (,1) 94 parts (1.0 mol) of phenol. 1

(2) 31.6 parts (0.25 mol) of'anhydroussodium ,sulfite (3) 27.4 parts (0.25 mol) of 95% sodium'bisulflte (4) 203.0 (2.5 mole) of 37% aqueousformalde hyde The above ingredients are brought together with cooling until the exothermic reaction subsides. The reaction mixture is then heated for 1.5 hours at SOP-95 C. after which the resulting syrup is heated for 0.5 hour with steam. The V15, cosity of the resulting syrup is about 10 poises as determined by a No. 300 Ostwald viscosimeter. Anion active resins to which the process of the present invention is applicable include those described in U. S. Patent Nos. 2,285,750, 2,395,825, 2,341,907, 2,402,384 and 2,251,234 as well as those described and claimed in my copending application with James R. Dudley, Serial No. 616,644, filed September 15, 1945. Other anion resins to which the process maybe applied include condensation products of acetaldehyde, formaldehyde and polyalkylene polyamines (Serial No. 643,836, filed January 26, 1946) of amino-triazine, aldehyde, and guanido compounds (Serial No. 607,277, filed July 26, 1945) of aminotriazine, aldehyde, strongly basic non-aromatic amines (Serial No. 649,127, filed February 20, 1946); of biguanide, carbonyl compounds and aldehydes (Serial No. 703,481, filed October 16, 1946) of crotonaldehyde, formaldehyde, and polyalkylene polyamines (Serial. ,No. 643,838, filed January 26, 1946) of polyepoxy compounds and alkylene polyamines (Serial No. 655,005, filed March 16, 1946); of glycerol dichlorohydrin and alkylene polyamines (Serial No.

624,606, filed October 25, 1945); of furfural,

guanido compounds and carbonyl compounds (Serial No. 703,489, filed October 16', 1946); and of furyl aliphatic amines and aldehydes (Serial No. 642,416, filed January 19, 1946).

Cation active resins to which the process of the present invention is applicable include those de-' scribed in U. S. Patents Nos. 2,228,159, 2,204,539,

fone, a Water-soluble sulfite and formaldehyde (Serial No. 694,817, filed September 4, 1946) sulfonated or phosphonated resinified furfural (Serial No. 652,355, filed March 5, 1946) etc.

In general, my process is applicable to any candensation type anion or cation active resin which has a sufficiently rapid gelation rate for bead formation. When the gelation rate is too slow, the resin globules agglomerate before they become hardened by gel formation.

Petroleum sulfonates generally are useful as the surface active agents in the present process. These petroleum sulfonates or white oil soaps are oil-soluble, water-dispersible organic sulfonates which are produced as by-produots in th.e. re. fining of petroleum distillates with sulfuric acid. I contemplate the use of'the alkali metal salts of the sulfonic acids which are produced in the distillates with fuming sulfuric acid. l 5 v wisest shouldpreierably boil a ov about;

1 have-spasms grammes sesame-1am equii 'a 6 tl'i'os' off the" fesin syrup, general-1y fi'bni The"-nf n-Sb1iieht mediamay' e afi as istofasingl-e eoi'n'ifiound or they maybe inik tu'res of we or more eomp'ounds as in Examples 2, 9 and if theprdDElti of the Combination fili't e 119665831? qualifications.

' Following" are some non-solvent inedi' present mve n Boiling Spec'ifie Point'C'H Gravity I87 71.143 123-.5' 1, 201 96.8' 1.159 3-: op'fvle 109 1:204 trichlorethyl eneu 87.2 1.466 1,1;2=,t'rieh10rethene. 113:5 "1. 441 1,1,1-trich1li'fethhne' T4. 1 1: 325 o-diehlorbenzene 179 L 305 e'th 8357 1.256 213 1144 6 .5 L14 p .130 1.226 fluoronaphthalene 212 1: 133 Hirotnbliexahe 156 1*:173 -hnqm ctane. .185; 1,99 l-brompropane .791 1.353 diph'enylethen 23;) 1.205

N n-se' ve iew ie rihe h ar f'e'rred 'speeific gnavity nay be diluted with less .den-se liquidssuehas toluene an-d/or Xylene until the density of; the Combination is substantially equivalent tothat of t'he' resin syfiip and til-eh used: satisfactorily in thepies'efitprdess. A few if these" ifldia 6f Hihfbedifib ilx' ity are.

' -soinngi r Gravity Fuithermoie; non-soltent iriedia of lower-than the pfef-ei' red' specific) gravity may alsobe iiised it other variables of the system in 'duestieniare e'eousiy be used in the pieeess-of modified to iecsustemu the effect-130i the density differential between the' iesin': and'the mm: solvent therefor. Such variablesinclude, for example, the efiicien-cy (rate and type) of. agitation which should he stepped up andith viseosity 9f nemesis syrup which 'shoiildfi'f' possible; be" heavier. A Preferredmedia-o'f lower specific gnaw ity include In the event that an extremely inert non-solvent medium is re uired, suitabl'eliquids include xylene hexafluoride, xylene hex-aehlo'ride, toluene trifiuo'ride; those-fluorearbons and fluorochloro earbons having the necessary-boiling point and specific gravity, n'i'ixtures' ofjthese inert media with each other and with 'other media mentioned above as suitable.

More specifically, in processes for beading resins which are sulfitedtmonnuc'lear sulion'ie acid groups) condensation products of phenol andieiimaiaen ae; the liquid-should boil above about 120 c. and bestable't'o'ifrom 9'0-f1'6'0" '0. because the i'esi'n'els slowly and is b'est'oui e'd at "a relatively, high temperat re. Nucl'earl'y sulforiated 'pnenbi-fsrmaidenyae condensation products," on the other" "eel vary r 113: and the; liquid "'mdmmneea therefore o'nl'yboil above "ensue "70 C. aimeugn' 'it' must be stable to from 9 0 -l'60 'C." ."for during purposes. Similarly,' anion resins which are as emerehyarinpo13 231163 1ene poljiam-i'ne o'rfufoi'fiialdhyde condensation liquid medium whiclilooil's aboile only about 70 C. and in addit'ion, the media for these resins portant. j :The "degree and type of agitation must be suificientnto keep the dispersion from coagu- Tati'hg but itnasa variabienppeel mn depending upon the size of beads d'es'iredandthe'piac tieality of .pi ed-ucingthem.- ;With-an an=chor type used in the examples, a speed of from H p 200' R! P. fgeneiallypre'ferredfor the iioioditetio'n' of resin "beads Within -arange suitable "for use --infi on-exc'h an'ge processes; "ire, from about 8 "6O I'ne'sh;wet sere'ened, on a standand U. S. Sieve Series U. S. Bureau of Standards, Standard Screen Series-1919). However, the speed can go as high as about 600 R. P. -M. in which case agrnuoh smallei' head is io'rined from a comparable ;resin syrup. Further-more, many cases variable speed-agitationgis desirable, gel formation being effected. at relatively low peejd' fb11 wedb$ increase'dsp' ed to "prevent aelg emera'tiim thee-spewed v idles mining the ure. annisner, impeller-bane, "turbine "and other a type agitating i means "ifiay be substituted fo t he anchortype ofthe'exainples.

;Wh'en extremely small or micro T beads are del d, as fo edieina'lij n exqhe eeepyiiefin' a high agitation rate with relatively large amounts of surface active agent are critical factors. In addition, as the rate of agitation is increased, the viscosity of the resin solution may need to be increased in order for bead formation to take place.

The success of my process appears to depend at least in part on the establishment, under any given set of conditions, of an interracial tension in the resin-medium system which is Within a definite range conducive to the formation of spheroidal particles. My process is specific to the particular type surface active agent claimed, however, since not all surface active agents which produce an interfacial tension within the predetermined range will necessarily work. I have i;

found that the cationic hydroxyalkyl amine salts and the quaternary ammonium salts disclosed in the present application are suitable for use in the preparation of phenol-formaldehyde condensation products containing omega sulfonic acid groups in spheroidal form according to the present process.

It may be desirable, according to the process of the present invention, to remove at least a portion of the water from the dispersed resin syrup in order to increase the reflux temperature of the system, particularly if the resin is to be cured in the non-solvent liquid or if it has a relatively slow rate of gelation. In some cases where the rate of gelation is extremely slow, i, e., nonnuclearly sulfonated phenol-formaldehyde resins, it is necessary to remove some water so that the resulting increased temperature will cause gelation before the globules or droplets agglomerate.

Once gelation has occurred and the resin beads are relatively hard and firm, the beads are cured by heating in the presence or absence of a nonsolvent liquid at from about 50-160 (3., the preferred curing temperature within the range depending upon the particular resin. For instance, I cure beads of epichlorohydrin-polyalkylene polyarnine resin at about 90130 0., preferably at about 100-125 6.; heads of guanidine-melamlneformaldehyde resin at about 50-110 C. and preferably in two stages, the first around 50 C. and

the second around 100 C. beads of nuclearly sulfonated and non-nuclearly sulfonated phenolformaldehyde resins at about 90-160 C., preferably at about 120-150 C.

The process of the present invention may be applied to the preparation of dyes, pigments, catalysts and ionic or non-ionic resinous materials in the form of spheroidal or micro spheroidal particles which, because of their spheroidal nature, possess special advantages over the corresponding granular products.

Similar processes applied to other type resins and/or other type surface active agents are described and claimed in the copending application of Arthur S. Nyquist, Serial No. 77,071, filed February 17, 1949, entitled Preparation of Non- Nuclearly Sulfonated Phenol-Formaldehyde Resin in Bead Form and in my copending applications Phenol-Formaldehyde Resin in Bead Form.

77,069". FebruarylT, 1949" Use of Non-Ionic Surface Active Agent in Preparation of Anionic Resin in Bead Form.

77,068. February 17, 1949.. Use of Cationic Surface Active Agent in Preparation of Anionic Resin in Bead Form.

I claim:

1. A process which comprises dispersing an aqueous syrup of a partially condensed resin oapable of being cured to a water-insoluble ion active product in an inert organic non-solvent liquid which has a boiling point of above about 70 C. and the density of which substantially equivalent to that of said aqueous resinous syrup. with mechanical agitation in the presence of an anionic surface active agent Which is a petroleum sulfonate, maintaining the dispersion at an elevated temperature until the resin gels, and finally curing the gelled resin obtained by heating, sufficient agitation being maintained throughout the heating to prevent coagulation of the dispersion.

2. A process which comprises dispersing an aqueous syrup of a partially condensed resin capable of being cured to a water-insolub1e product which is a condensation product of phenol and formaldehyde containing omega sulfonic acid groups in an inert, organic non-solvent liquid which has a boiling point of at least 120 C. and the density of which is substantially equivalent to that of said aqueous resin syrup, with mechanical agitation in the presence of an anionic surface active agent which is a petroleum sulfonate, heating the dispersion to azeotropically remove water from the dispersed resin globules until the temperature of gelation 0f the resin i attained, and finally curing the gelled resin obtained by heating, sufficient agitation being maintained throughout the heating to prevent coagulation of the dispersion.

3. A process which comprises dispersing an aqueous syrup of a partially condensed resin capable of being cured to a water-insoluble anion active product in an inert organic non-solvent liquid which has a boiling point of at least 120 C. and the density of Which is substantially equivalent to that of said aqueous resin syrup, with mechanical agitation in the presence of an anionic surface active agent which is a petroleum sulfonate, maintaining the dispersion at an e evated temperature until the resin gels, and finally curingthe gelled resin obtained by heating, suflicient agitation being maintained throughout the heating to prevent coagulation of the dispersion.

l. A process according to claim 1 in which the non-solvent liquid is a chlorinated hydrocarbon. 5. A process in accordance with claim 3 in which the anion active material is a condensation product of epichlorohydrin and a polyalkylene polyamine.

LEN'NAR'I A. LUNDBERG.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PA'IENTS 

1. A PROCESS WHICH COMPRISES DISPERSING AN AQUEOUS SYRUP OF A PARTIALLY CONDENSED RESIN CAPABLE OF BEING CURED TO A WATER-INSOLUBLE ION ACTIVE PRODUCT IN AN INERT ORGANIC NON-SOLVENT LIQUID WHICH HAS A BOILING POINT OF ABOVE ABOUT 70* C. AND THE DENSITY OF WHICH IS SUBSTANTIALLY EQUIVALENT TO THAT OF SAID AQUEOUS RESINOUS SYRUP, WITH MECHANICAL AGITATION IN THE PRESENCE OF AN ANIONIC SURFACE ACTIVE AGENT WHICH IS A PETROLEUM SULFONATE, MAINTAINING THE DISPERSION AT AN ELEVATED TEMPERATURE UNTIL THE RESIN GELS, AND FINALLY CURING THE GELLED RESIN OBTAINED BY HEATING, SUFFICIENT AGITATION BEING MAINTAINED THROUGHOUT THE HEATING TO PREVENT COAGULATION OF THE DISPERSION. 